Zr改性Ni_2P/SBA-15催化剂的制备及其加氢脱氧性能
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摘要
以正丙醇锆(n)和Zr(SO_4)_2(m)为锆源制备了Zr改性的Ni_2P/ZrO_2-SBA-15(n)和Ni_2P/ZrO_2-SBA-15(m)催化剂,并采用XRD、BET、CO吸附、XPS、NH_3程序升温脱附等手段对催化剂进行了表征。以苯并呋喃(BF)为模型化合物,研究了催化剂加氢脱氧(HDO)性能。结果表明,Zr改性后,形成了新的层状结构的ZrP;Zr的引入有助于生成更多、更小粒径的Ni_2P活性相,催化剂的酸强度和酸量均提高。与正丙醇锆相比,Zr(SO_4)_2为锆源能够获得比表面积大、酸性强、酸量大的催化剂,得到更多的ZrP相、更小粒径的Ni_2P晶粒,暴露更多的Ni活性位点。Ni_2P/ZrO_2-SBA-15(n)和Ni_2P/ZrO_2-SBA-15(m)的BFHDO产率分别为71.5%和85.9%,较Ni_2P/SBA-15分别提高了14.0%和28.4%。催化剂HDO活性、脱氧产物选择性和产率大小顺序为:Ni_2P/ZrO_2-SBA-15(m)>Ni_2P/ZrO_2-SBA-15(n)>Ni_2P/SBA-15。
Ni_2P/ZrO_2-SBA-15(n) and Ni_2P/ZrO_2-SBA-15( m) catalysts were prepared from n-propoxide zirconium( n) and Zr( SO_4)_2( m) as zirconium sources. The catalysts were characterized by X-ray diffraction( XRD), N2 adsorption specific surface area measurements( BET), CO uptake, X-ray photoelectron spectroscopy( XPS) and NH_3 temperature programmed desorption( NH_3-TPD). The results showthat after Zr modification,a newlayered structure of ZrP is formed. The introduction of Zr helps to generate more Ni_2P active phase with smaller crystal size,and increase both the acid strength and acid amount of the catalyst. Compared with zirconium n-propoxide,the catalyst prepared from Zr( SO_4)_2 has larger specific surface area,more acid amount,stronger acidity,more Zr P phases,smaller Ni_2P crystal grains and more Ni active sites. The product yields of benzofuran hydrodeoxygenation( BF HDO) given by Ni_2P/ZrO_2-SBA-15( n) and Ni_2P/ZrO_2-SBA-15( m) were 71.5% and 85.9% respectively,which were increased by 14.0% and 28.4% respectively compared with Ni_2P/SBA-15. The BF HDO activity,selectivity and yield of the BF HDO products decreased in the order of Ni_2P/ZrO_2-SBA-15( m) > Ni_2P/ZrO_2-SBA-15( n) >Ni_2P/SBA-15.
Ni_2P/ZrO_2-SBA-15(n) and Ni_2P/ZrO_2-SBA-15( m) catalysts were prepared from n-propoxide zirconium( n) and Zr( SO_4)_2( m) as zirconium sources. The catalysts were characterized by X-ray diffraction( XRD), N2 adsorption specific surface area measurements( BET), CO uptake, X-ray photoelectron spectroscopy( XPS) and NH_3 temperature programmed desorption( NH_3-TPD). The results showthat after Zr modification,a newlayered structure of ZrP is formed. The introduction of Zr helps to generate more Ni_2P active phase with smaller crystal size,and increase both the acid strength and acid amount of the catalyst. Compared with zirconium n-propoxide,the catalyst prepared from Zr( SO_4)_2 has larger specific surface area,more acid amount,stronger acidity,more Zr P phases,smaller Ni_2P crystal grains and more Ni active sites. The product yields of benzofuran hydrodeoxygenation( BF HDO) given by Ni_2P/ZrO_2-SBA-15( n) and Ni_2P/ZrO_2-SBA-15( m) were 71.5% and 85.9% respectively,which were increased by 14.0% and 28.4% respectively compared with Ni_2P/SBA-15. The BF HDO activity,selectivity and yield of the BF HDO products decreased in the order of Ni_2P/ZrO_2-SBA-15( m) > Ni_2P/ZrO_2-SBA-15( n) >Ni_2P/SBA-15.
引文
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[2]SONG H,GONG J,SONG H,LI F,ZHANG J,CHENG Y.Preparation of core-shell structured Ni2P/Al2O3@Ti O2and its hydrodeoxygenation performance for benzofuran[J].Catal Commun,2016,85:1-4.
[3]CZERNIK S,BRIDGWATER A V.Overview of applications of biomass fast pyrolysis oil[J].Energy Fuels,2004,18(2):590-598.
[4]GOYAL H B,SEAL D,SAXENA R C.Bio-Fuels from thermochemical conversion of renewable resources:A review[J].Renewable Sustainable Energy Rev,2008,12(2):504-517.
[5]GRALDINE L,SOIZIC B,JULIE R,FRDRIC R,ANNE S M,LAURENCE C,ANNIE P,MICHEL R,SYLVETTE B.Effect of the presence of ionic liquid during the Ni M o S bulk preparation in the transformation of decanoic acid[J].Appl Catal A:Gen,2017,532:120-132.
[6]ZHAO H Y,LI D,BUI P,OYAMA S T.Hydrodeoxygenation of guaiacol as model compound for pyrolysis oil on transition metal phosphide hydroprocessing catalysts[J].Appl Catal A:Gen,2011,391(1/2):305-310.
[7]MA H,LI Q,SHI Y,SUN X.Ni2P/Zr O2-SBA-15 dibenzothiophene hydrodesulfurization catalysts:Preparation,characterization and evaluation[J].Trans Tianjin Univ,2017:1-11.
[8]LUO N,CAO Y,LI J,GUO W,ZHAO Z.Preparation of Ni2P/Zr O2-M CM-41 catalyst and its performance in the hydrodeoxygenation of Jatropha curcas oil[J].Chem Technol Fuels Oil,2016,44(1):76-83.
[9]LIU D,WANG A,LIU C,ROEL P.Ni2P/Al2O3hydrodesulfurization catalysts prepared by separating the nickel compound and hypophosphite[J].Catal Today,2017,292:133-142.
[10]FAN G,SHEN M,ZHANG Z,FARUI J.Preparation characterization and catalytic properties of S2O2-8/Zr O2-Ce O2solid superacid catalyst[J].J Rare Earth,2009,27(3):437-442.
[11]LAYMAN K A,BUSSELL M E.Infrared spectroscopic investigation of CO adsorption on silica-supported nickel phosphide catalysts[J].J Phys Chem B,2004,108(30):10930-10941.
[12]LEE Y K,OYAMA S T.Comparison of structural properties of Si O2,Al2O3,and C/Al2O3supported Ni2P catalysts[J].Stud Surf Sci Catal,2006,159:357-360.
[13]CECILIA J A,INFANTES M A,RODRGUEZ C E,JIMNEZ L A.A novel method for preparing an active nickel phosphide catalyst for HDS of dibenzothiophene[J].J Catal,2009,263(J):4-15.
[14]GALTAYRIES A,SPORKEN R,RIGA J,BLANCHARD G,CAUDANO R.XPS comparative study of ceria/zirconia mixed oxides:pow ders and thin film characterisation[J].J Electron Spectrosc,1998,88:951-956.
[15]PAN B,ZHANG Q,DU W,ZHANG W,PAN B,ZHANG Q,XU Z,ZHANG Q.Selective heavy metals removal from waters by amorphous zirconium phosphate:Behavior and mechanism[J].Water Res,2007,41(14):3103-3111.
[16]LI K,WANG R J,CHEN J X.Hydrodeoxygenation of anisole over silica-supported Ni2P,M o P,and Ni M o P catalysts[J].Energy Fuels,2011,25:854-863.
[17]ZHU T,SONG H,DAI X,SONG H.Preparation of Ni2P/Al-SBA-15 catalyst and its performance for benzofuran hydrodeoxygenation[J]Chin J Chem Eng,2017,25(12):1784-1790.
[18]LAN L,GE S,LIU K,HOU Y,BAO X.Synthesis of Ni2P promoted trimetallic Ni M o W/γ-Al2O3catalysts for diesel oil hydrotreatment[J].J Nat Gas Chem,2011,20:117-122.
[19]MOON J S,KIM E G,LEE Y K.Active sites of Ni2P/Si O2catalyst for hydrodeoxygenation of guaiacol:A joint XAFS and DFT study[J].J Catal,2014,311:144-152.
[20]LEE C L,OLLIS D F.Catalytic hydrodeoxygenation of benzofuran and o-ethylphenol[J].J Catal,1984,87(2):325-331.
[21]BENSON S W.Thermochemical Kinetics[M].New York:Wiley,1968:23-32.
[22]GONALVES V O O,DE SOUZA P M,DA SILVA V T,NORONHA F B,RICHARD F.Kinetics of the hydrodeoxygenation of cresol isomers over Ni2P/Si O2:Proposals of nature of deoxygenation active sites based on an experimental study[J].Appl Catal B:Environ,2017,205:357-367.